PROCESS FOR THE OLIGOMERISATION OF OLEFINS

Description

[0001] This invention relates to a process for the manufacture of higher molecular weight organic molecules from lower molecular weight materials, especially olefins, by oligomerization, to crystalline molecular sieves suitable for use in the process, and the use of such molecular sieves in such reactions. The invention also relates to the production of derivatives from the oligomers produced and their use as feedstocks for further reactions.

[0002] Molecular sieve catalysts of many types have been used, or proposed for use, in numerous chemical processes. Commercially, they have been used, for example, in hydrocarbon dewaxing, hydrocracking, toluene disproportionation, and alkylation of aromatics. Among processes for which they have been proposed in the literature is the conversion by oligomerization of lower olefins, e.g., alkenes, to higher olefins, e.g., higher alkenes, for example the oligomerization of C₂ to C₆, especially C₃ and C₄, olefins to olefins in the C₆ to C₁₂ range, and occasionally higher.

[0003] An example of a proposal to use crystalline molecular sieves as catalysts for oligomerization is that described in EP-B-625 132, where a hydrated olefinic feedstock is oligomerized over a zeolite catalyst, the water content of the feedstock being from 0.05 to 0.25 molar percent. The process is said to result in an increase in yield of higher molecular weight alkenes and to have the additional advantage of enabling the reaction to be carried out at relatively low temperatures. WO 94/12452 proposes the production of at least one C4 and C5 branched olefin by passing a feedstock containing ethene and at least one C3 to C10 olefin over a zeo-type catalyst having a framework structure which includes a 10-member channel that is not intersected by another 10- or 12- member channel. The process is said to achieve higher conversions of the ethene feed. Another example of such a proposal is that described in EP-B-746 538, where zeolites of the structure types MFI, TON, and MFS, in their acid forms, are used in oligomerization of propene and butene, the particular members of those structure type families used being ZSM-5, ZSM-22, and ZSM-57. The patent is concerned with controlling the extent of oligomerization, to obtain the desired proportions of or selectivity to dimer, trimer, and higher oligomers, for use in downstream manufacturing processes. In the patent, methods of improving trimer yield are described, the observation being made that higher conversion rates produce an oligomer mixture with a lower degree of branching.

[0004] The use of crystalline molecular sieves as catalysts has been found, however, to be subject to certain limitations in practice. The feedstocks used are frequently refinery products and may contain sulphur compounds. In commercial processes customarily using such feedstocks as, for example, alkylation of aromatics and toluene disproportion sulphur has to be removed before the feedstock contacts the catalyst. Exceptionally, if the feed contains hydrogen as, for example, in dewaxing and hydrocracking, sulphur removal may not be necessary as the hydrogen present appears to stabilize the catalyst.

[0005] Our experiments have shown that under conditions normally used for olefin oligomerization over molecular sieve catalysts, sulphur-containing feedstocks may reduce catalyst activity and lifetime. However, it has now surprisingly been found that the presence of sulphur does not appear to have adverse effects on the reaction process itself. Indeed, provided oligomerization is carried out at a temperature higher than that which would otherwise have been chosen for the reaction concerned, the effect on catalyst activity and life may be mitigated, minimal, or even of advantage.

[0006] The temperature appropriate to mitigate the adverse effects of sulphur compounds will vary, depending on the catalyst being used, the olefinic species being oligomerized, the specific sulphur compound or compounds and their proportions present in the feedstocks. An appropriate minimum temperature may, however, be readily identified by routine experiment.

[0007] The present invention accordingly provides a process for the oligomerization of an olefinic feedstock which comprises contacting under oligomerization conditions an olefinic feedstock containing from 1 to 100 ppm by volume of sulphur-containing compounds with a catalyst comprising at least one crystalline molecular sieve selected from sieves having the TON and MFS structure types, and recovering a product containing at least one olefin oligomer, whereby the process is carried out at a temperature of from at least 160°C to 350°C and if a sieve of the TON structure type is selected, at least 190°C.

[0008] In this specification, the term "structure type" is used in the sense described in the Structure Type Atlas, Zeolites 17, 1996. Examples of TON structure type zeolites include ZSM-22, ISI-1, Theta-1, Nu-10, and KZ-2, and of MFS include ZSM-57, all preferably in their H- or acid form.

[0009] The crystalline molecular sieve is advantageously ZSM-22 or ZSM-57. ZSM-22 and its manufacture are described in, for example, U.S. Patent No. 4 556 477 and WO 93/25475, and ZSM-57 and its manufacture in EP-A-174 121 and U.S. Patent No. 4 973 870. Mixtures of two or more molecular sieves may be used, e.g., a mixture of ZSM-22 and ZSM-57.

[0010] A molecular sieve crystallite size advantageously up to 5µm, preferably within the range of from 0.05 to 5µm, more especially from 0.05 to 2µm, and most preferably from 0.1 to 1µm, may be employed. The molecular sieve may be supported or unsupported, for example in powder form, or used as an extrudate with an appropriate binder. An as-synthesized molecular sieve is advantageously converted to its acid form, for example by acid treatment, e.g., by HCl, or by ammonium ion exchange, and subsequent calcination before use in the process of the invention. The calcined materials may be post-treated as by steaming. Although the invention will be described with reference to zeolites proper, it is possible to use, as is known in the art, a material in which silicon and aluminium have been replaced in whole or in part by other elements, silicon more especially by germanium or phosphorus and aluminium more especially by boron, gallium, chromium and iron, materials containing such replacement lattice elements also being termed zeolites, and the term is used in the broader sense in this specification.

[0011] The olefin feedstock advantageously contains olefins having from 2 to 12 carbon atoms, preferably from 2 to 6 carbon atoms, and is advantageously an alkene-containing feedstock. The feedstock itself may be or comprise an oligomer, especially a dimer, especially one provided by recycling a part of a product stream. The feed preferably contains propene, butenes, pentenes and/or hexenes; the invention is especially applicable to propene and butene oligomerization.

[0012] As indicated above, the feedstock contains sulphur-containing compounds within the range of from 1 to 100, more advantageously up to 50, still more advantageously up to 30, preferably up to 20, more preferably up to 5, and still more preferably up to 2, ppm by volume of such compounds. It is within the scope of the invention to reduce the proportion of sulphur compounds from above the upper end of any of the given ranges, for example about 200 ppm, to within any of the ranges, and also to reduce the proportion from within a less preferred range to a more preferred range. A typically encountered feedstock may have from 1 to 30 or from 2 to 20 ppm by volume of sulphur compounds, and the invention is well suited to such feedstocks.

[0013] The sulphur content is conveniently ascertained by gas chromatographic analysis using peak areas normalized with reference to a COS standard.

[0014] As examples of sulphur-containing compounds, there may be mentioned, more especially, saturated aliphatic compounds, for example, thiols, sulphides, including cyclic sulphides, and disulphides. Typical compounds include, for example, hydrogen sulphide, dimethyl sulphide, diethyl sulphide, ethyl methyl sulphide, n-propyl sulphide, 1- and 2-propanethiols, 1-butanethiol, 1,1-methylethylthiol, ethyl methyl disulphide, dimethyl disulphide and tetrahydrothiophene.

[0015] Reaction conditions for the process of the invention may be, with the exception of the temperature and the presence of the sulphur compound or compounds, in accordance with conditions operative for prior art processes for oligomerization of the same olefin or olefins.

[0016] The olefinic feedstock may be fed to the reaction zone in the liquid or, preferably, the supercritical phase. The feedstock may contain water, either present from the feedstock raw material or by addition.

[0017] The feedstock advantageously comprises from 0.05 to 0.25, preferably from 0.06 to 0.20 and more preferably from 0.10 to 0.20, molar % water based on the total hydrocarbon content of the feedstock. If desired or required, the natural water content of the feedstock may be increased, for example, by being passed through a thermostatted water saturator. Since the amount of water required to saturate the feedstock will depend upon the temperature and composition of the feedstock, control of the water content may be effected by appropriate control of the temperature of the feedstock.

[0018] The feedstock may also comprise an inert diluent, for example, a saturated hydrocarbon. That other hydrocarbon is included in the hydrocarbon content for the purposes of calculation of the water content.

[0019] Operating temperatures for olefin oligomerization have variously been reported in the literature as being between 80°C and 350°C. Toward and above the upper end of the range, de-oligomerization rates increase and may predominate over the oligomerization reaction, providing the upper limit to practical operation.

[0020] As indicated above, once the person skilled in the art is in possession of the invention, it is a matter of routine experiment to ascertain, for a given feedstock and catalyst, the minimum and optimum temperatures for operation within the general ranges of 160°C to 350°C. The following combinations are given as examples only.

[0021] In MFS (typically ZSM-57)-catalysed reactions, an operating temperature of at least 160°C and up to about 220°C is advantageous, at least 170°C is preferred, and at least 200°C is more preferred. An MFS catalyst is preferred when the feedstock is propene and the target oligomers are nonenes.

[0022] In TON (typically ZSM-22)-catalysed reactions, an operating temperature of at least 190°C, preferably 200°C, is advantageous, at least 220°C is preferred, and at least 250°C is more preferred. The upper limit is 350°C; a preferred upper limit is 300°C. A TON catalyst is preferred when the feedstock is butene and the target oligomers are low-branched octenes.

[0023] It will be appreciated that, to maintain desirable conversion rates, it may be advantageous to increase reaction temperatures with the time the catalyst is on stream.

[0024] The pressure is advantageously in the range of 5 to 10 MPa, preferably from 6 to 8 MPa. The olefin hourly space velocity is advantageously in the range of from 0.1 to 20, preferably from 1 to 10, and more preferably from 1.5 to 7.5, hr^-1.

[0025] When the oligomer product is to be used as starting material for certain purposes, e.g., in the manufacture of certain plasticizer or detergent grade alcohols, it is desirable to minimize the degree of branching of the product.

[0026] The degree of branching of the olefin oligomer may be controlled to some extent by operating temperature, higher temperatures normally yielding a lower degree of branching (branchiness). The olefin branchiness largely determines that of any downstream product, for example plasticizer or detergent grade alcohols, produced, for example, by the oxo process, from the oligomer olefins. The users of such products, and in turn their downstream products, for example plasticizer esters, have strict specifications for various properties which the suppliers have to meet, and these specifications typically require branchiness to be within a defined range, usually a low range.

[0027] However, when an oligomerization operation is started up using fresh catalyst, the catalyst is highly active and, since the oligomerization is exothermic, there is a serious risk of reactor runaway. It is therefore normally necessary to operate initially at a low temperature and only reach the desired operating temperature over a prolonged period, during which substantial quantities of product are produced. This portion of the product will be of greater branchiness than that produced later, thereby increasing the average branchiness of the product, increasing the difficulty of meeting the customer's specification.

[0028] It has surprisingly been found that using a sulphur-containing feed as described herein in some way controls the initial over-activity of the catalyst, enabling the reaction to be started up at, or close to, the desired operating temperature.

[0029] The invention accordingly also provides a process for controlling the activity in an oligomerization reaction of a catalyst comprising at least one crystalline molecular sieve selected from sieves of the TON and MFS structure types, which comprises contacting the molecular sieve with a sulphur compound-containing olefinic feedstock, whereby the process is carried out at a temperature of from at least 160°C to 350°C and if a sieve of the TON structure type is selected, at least 190°C.

[0030] The invention accordingly also provides a process for controlling the degree of branching of the product of an oligomerization reaction which comprises contacting under oligomerization conditions a sulphur compound-containing olefinic feedstock with a catalyst comprising at least one crystalline molecular sieve selected from sieves having the TON and MFS structure types, whereby the process is carried out at a temperature of from at least 160°C to 350°C and if a sieve of the TON structure type is selected, at least 190°C.

[0031] The invention accordingly also provides the use of an elevated temperature in such a reaction to control the degree of branching of the oligomeric product.

[0032] Advantageously, the sulphur content of the feedstock is from 1 to 100 ppm by volume.

[0033] The effect on the degree of branching is especially evident when the feedstock is propene; with ZSM-22, the branchiness of the trimer is significantly reduced; with ZSM-57, branchiness of both dimer and trimer is reduced.

[0034] The present invention also provides the use in an oligomerization reaction of a crystalline molecular sieve of the TON or MFS structure type having absorbed therein or adsorbed thereon at least one sulphur-containing compound. Advantageously, the crystalline molecular sieve is ZSM-22 or ZSM-57. Advantageously, the sulphur compound is, or is derived from, one of the groups specified above, and preferably is, or is derived from, one of the specific compounds identified above. Advantageously, the crystalline molecular sieve having a sulphur-containing compound absorbed therein or adsorbed thereon is one obtainable by, and preferably one obtained by, use as an oligomerization catalyst for a sulphur compound-containing feedstock.

[0035] The oligomers produced by the process of the present invention are a unique mixture of isomers, the members of which fall into five types of skeletal structures, which are

Type I RCH = CH₂

Type II RCH = CHR'

Type III RRC = CH₂

Type IV RR'C = CHR"

Type V RR' C = CR"R"'

where R, R', R" and R"' are alkyl groups. The olefin type may be identified by proton NMR analysis. Especially in combination with the controlled average degree of branching, the oligomer products of the invention have advantages over those produced by traditional, e.g., supported phosphoric acid catalysed, processes. These are primarily a lower average degree of branching, and a lower proportion of Type V olefins, making them more suitable for onward processing, e.g., higher alcohol, aldehyde, and acid manufacture, because of a desirable reactivity when the oligomeric composition is subjected to the oxo process (hydroformylation).

[0036] The present invention accordingly also provides for the production of an alcohol from an oligomeric hexene mixture having an average degree of branching of at most 0.95, especially one within the range of from 0.92 to 0.95, and a maximum Type V content of 6%, preferably 5%.

[0037] The present invention further provides for the production of an alcohol from an oligomeric nonene mixture having an average degree of branching of at most 2.0, and advantageously in the range of 1.5, preferably 1.78, to 2.0, more advantageously 1.78 to 1.86, and having a type V olefin content of at most 14%, preferably within the range of 10 to 14%, especially one obtainable by ZSM-22 catalysed oligomerization, especially in the presence of sulphur. Advantageously, the Type IV olefin content is within the range of 58 to 60%; advantageously the Type III olefin content is within the range of 7.25 to 7.75%; , advantageously the Type II olefin content is within the range of 18.5 to 20%, and advantageously the Type I olefin content is 1.2 to 2.2%.

[0038] The invention further provides for the production of an alcohol from an oligomeric dodecene mixture having an average degree of branching of at most 2.75, advantageously in the range of 2.70 to 2.75, and advantageously one having a type V olefin content of at most 19%, and preferably within the range of from 16 to 19%, especially one obtainable by ZSM-22 catalysed oligomerization, especially of propene, especially in the presence of sulphur. Advantageously, the type IV olefin content is within the range of 59 to 62%; advantageously the Type III olefin content is within the range 4.8 to 5.7%; and advantageously the Type II olefin content is within the range 14 to 15%.

[0039] As indicated above, the oligomers of the invention are especially suitable as feedstocks for further processing, including at least one of the following: fractionation; hydrogenation; hydroformylation; oxidation; carbonylation; etherification; epoxidation, and hydration. The hydrogenated oligomeric octenes may comprise, for example, 12 to 15% 2-methylheptane; 22 to 28% 3-methylheptane; and 7 to 9% 4-methylheptane. These are especially readily obtainable by oligomerization using a catalyst comprising ZSM-22.

[0040] The eventual products may be alcohols, produced for example by hydroformylation and hydrogenation; esters, in which the alcohols are esterified as with inorganic or organic acids, including carboxylic acids, especially polycarboxylic acids; aldehydes, acids, in which the hydroformylation products are oxidized and hydrogenated, and numerous other end uses.

[0041] The esters with polycarboxylic acids are especially valuable as plasticizers, and the invention further provides for producing plasticizer compositions comprising the esters, and polymeric compositions, especially of vinyl polymers, more especially PVC, comprising the esters, and shaped structures formed of the plasticized polymeric compositions.

Examples

[0042] The following examples, in which parts and percentages are by weight unless otherwise indicated, illustrate the invention.

[0043] All feeds used in the examples were hydrated by passage through a water saturator at 25° to 40°C.

[0044] Olefin monomer conversion rates were derived from gas chromatographic analysis using peak areas normalized to the total sum of the paraffins in the feed as internal standard, conversion being expressed as:

where A represents chromatographic peak area in product (wt%), A° represents chromatographic peak area in feed (wt%) and o.m. represents olefin monomer(s).

[0045] Selectivity to a given oligomer (dimer, trimer, etc.) is also determined from gas chromatographic peak areas, after hydrogenation of the product stream.

Example 1

[0046] In this example, butene oligomerization was carried out over a commercial ZSM-22 catalyst (ZSM-22 (75%) supported on alumina), at a weight hourly space velocity of 6.8h^-1, on a 60 to 65% butenes/35 to 40% butane feedstock hydrated by passing through water at 40°C. The reactor effluent was analysed by gas chromatrography (GC), feed and product olefin/paraffin ratios being compared to determine conversion. Liquid product was analysed on GC equipment having a platinum catalyst to hydrogenate olefins to paraffin, carbon number and skeleton being determined. In Comparative Samples C1 and C3 a pure (i.e., sulphur-free) butene feed was used, in Examples 1 and 1' a refinery feedstock containing 20 ppm sulphur (16 ppm dimethylsulphide, 1.5 ppm diethyl sulphide, remainder methylethylsulphide and mercaptans) was used.

[0047] The results are shown in the table below.

Sample	C1	1'	C3	1
Sulphur, ppm	0	20	0	20
Temperature, °C	225	217	280	281
Days On Steam	7	7	13.6	13.6
Total Conversion, %	50.76	33.27	93.04	91.45
Product Mix, %
C4	2.5	2.58	2.7	1.62
C5	0.77	0.92	0.96	0.92
C6	0.15	0.14	0.41	0.37
C7	0.26	0.2	1.15	0.97
C8	66.11	71.66	50.77	52.48
C9	1.86	2.03	2.8	2.5
C10	0.63	0.66	1.9	1.81
C11
C12	17.21	13.69	25.8	25.29
C13	1	0.88	1.74	1.6
C14
C15
C16	9.51	7.24	11.78	12.44
Sum	97.5	97.42	97.31	98.38
C7-C9, %	70	76	56	57
C10-C13, %	19	16	30	29
C13 +, %	10	07	12	13
C8/(C7 + C8 + C9)	96.9	97	92.8	93.8

[0048] Comparative example 1 and example 1' show that catalyst activity is significantly reduced by the presence of sulphur at lower operating temperatures (about 220°C) whereas as shown by Comparative Sample 3 and Example 1 the negative effects of sulphur are avoided at 280°C.

[0049] The carbon skeletons of the products, after hydrogenation, are shown in the table below.

Example	C1	1'	C3	1
Run
2,2,4-tri-Me-pentane	0.72	1.1	0.39	41
2,2-di-Me-hexane	1.17	1.16	1.8	1.8
2,5-di-Me-hexane	2.83	1.5	9.29	8.99
2,4-di-Me-hexane	11.74	11.88	16.89	16.84
3,3-di-Me-hexane	1.86	2.74	0.97	0.95
2,3,4-tri-Me-pentane	3.66	5.28	1.61	1.76
2,3,3-tri-Me-pentane	0.95	1.5	3	0.32
2,3-di-Me-hexane	6.29	6.44	8.61	8.75
2-Me-3-Et-pentane	2.77	3.62	2.02	2.08
2-Me-heptane	13.17	9.34	14.22	14.15
4-Me-heptane	7.48	5.27	7.85	7.8
3,4-di-Me-hexane	18.57	28.75	6.17	6.47
3-Me-heptane	23.63	17.11	24.73	24.55
n-Octane	5.15	4.32	5.17	5.11
C8 Linear	5.15	4.32	5.17	5.11
C8 Mono-branched	44.27	31.72	46.8	46.5
C8 Di-branched	45.24	56.08	45.74	45.89
C8 Tri-branched	5.34	7.88	2.29	2.49
C8 Branchiness	1.51	1.68	1.45	1.46

Example 2

[0050] This example illustrates the influence of sulphur on the activity of a ZSM-57 catalyst in propene oligomerization and the effect of an elevated temperature on that influence.

[0051] A 50% ZSM-57/50% alumina catalyst was used to oligomerize a sulphur-free feedstock of 50% propene/50% butanes at 135°C, at a WHSV of 2.02. The product stream contained about 73% nonenes, 9% dodecenes and 7% hexenes at a total conversion rate of 88%, average degree of branching of the nonenes 1.99.

[0052] 2 ppm of dimethyldisulphide were added to the feedstock and the run continued under otherwise the same conditions. Over the course of 24 hours, the catalyst was nearly completely deactivated, shown by a fall in the conversion rate to 5%.

[0053] The temperature was then raised to 175°C, when the catalyst recovered and the conversion rate rose to 95%. The product stream contained about 64% nonenes, 11% dodecenes and 5% hexenes, average degree of branching of the nonenes 1.95.

[0054] The example shows that an elevated temperature avoids the deleterious effects of sulphur on the activity of the crystalline molecular sieve catalyst, and is effective to reactivate a de-activated catalyst.

Example 3

[0055] To the pure feedstock of Example 2 were added 7 ppm ethyl sulphide and oligomerization was carried out at 168°C over the catalyst used in that example. The product stream contained about 66% nonenes, 11% dodecenes and 9% hexenes, branchiness of the nonenes 2.0. The conversion rate was 93%.

[0056] It was found, using sulphur-free feed, that oligomerizing propene over ZSM-22 at 255°C yielded a nonene product of branchiness 1.57, with 40% of mono-branched isomers. Similarly, using ZSM-22 at 277°C, a sulphur-free butene feed yielded an octene product of branchiness 1.15, with 66% mono-branched isomers. A sulphur-containing feedstock would yield similar results.

Claims

1. A process for the oligomerization of an olefinic feedstock which comprises contacting under oligomerization conditions an olefmic feedstock containing from 1 to 100 ppm by volume of sulphur-containing compounds with a catalyst comprising at least one crystalline molecular sieve selected from sieves of the TON and MFS structure types, and recovering a product containing at least one olefin oligomer, whereby the process is carried out at a temperature of from at least 160°C to 350°C and if a sieve of the TON structure type is selected, at least 190°C.

2. The process as claimed in claim 1, wherein the feedstock comprises at least one olefin having from 2 to 12 carbon atoms.

3. The process as claimed in claim 2, wherein the feedstock comprises at least one alkene selected from propene and butenes.

4. The process as claimed in any preceding claim carried out using a catalyst comprising an MFS structure type molecular sieve.

5. The process as claimed in claim 4, carried out at at least 170°C.

6. The process as claimed in claim 5, carried out at at least 220°C.

7. The process as claimed in any one of claims 1 to 6, wherein the crystalline molecular sieve is H-ZSM-57.

8. The process as claimed in any one of claims 1 to 3, carried out using a catalyst comprising a TON structure type molecular sieve at a temperature of at least 200°C.

9. The process as claimed in claim 8, carried out at a temperature of at least 220°C.

10. The process as claimed in claim 9, carried out at a temperature of at least 250°C.

11. The process as claimed in any one of claims 1 to 3 or any one of claims 8 to 10, wherein the crystalline molecular sieve is H-ZSM-22.

12. The process as claimed in claim 7 or claim 11, wherein the crystalline molecular sieve comprises a mixture of H-ZSM-22 and H-ZSM-57.

13. The process as claimed in any preceding claim, wherein the crystalline molecular sieve is in powder form or in the form of an extrudate.

14. The process as claimed in any preceding claim, wherein the content of sulphur-containing component is within the range of 1 to 50 ppm by volume.

15. The process as claimed in claim 14, wherein the content is within the range of 1 to 30 ppm.

16. The process as claimed in claim 15, wherein the content is within the range of 1 to 20 ppm.

17. The process as claimed in any preceding claim, wherein the sulphur content of the feedstock has been reduced prior to subjecting the feedstock to oligomerization.

18. The process as claimed in any preceding claim, wherein the sulphur-containing compound comprises at least one compound selected from hydrogen sulphide, dimethyl sulphide, diethyl sulphide, ethyl methyl sulphide, n-propyl sulphide, 1- and 2-propanethiols, 1-butanethiol, 1,1-methylethylthiol, ethyl methyl disulphide, dimethyl disulphide and tetrahydrothiophene.

19. The process as claimed in any preceding claim, wherein the feedstock is hydrated.

20. The process as claimed in any preceding claim wherein the feedstock is or comprises an oligomer.

21. The use of the process according to claim 1 for controlling the degree of branching of the product of an oligomerization reaction.

22. The use of the process according to claim 1 for controlling the activity of the catalyst in an oligomerization reaction.

23. The process according to any one of claims 1 to 19 further comprising subjecting the oligomerization product to hydroformylation and hydrogenating the hydroformylation product to produce an alcohol.

24. The process as claimed in claim 23 further comprising esterifying the alcohol to produce an ester.

25. The process according to claim 24, wherein the ester of the alcohol is with a polycarboxylic acid, further comprising incorporating the ester into a plasticizer composition.

26. The process according to claim 25 further comprising incorporating the plasticizer composition into a polymeric composition.

Ansprüche

1. Verfahren zur Oligomerisierung eines olefinischen Eins atzmaterials, bei dem unter Oligomerisierungsbedingungen ein olefinisches Einsatzmaterial, das 1 bis 100 Vol.ppm schwefelhaltige Verunreinigungen enthält, mit einem Katalysator kontaktiert wird, der mindestens ein kristallines Molekularsieb ausgewählt aus Sieben der Strukturtypen TON und MFS umfasst, und ein Produkt gewonnen wird, das mindestens ein Olefinoligomer enthält, wobei das Verfahren bei einer Temperatur von mindestens 160°C bis 350°C und bei Auswahl eines Siebs vom Strukturtyp TON mindestens 190°C durchgeführt wird.

2. Verfahren nach Anspruch 1, bei dem das Einsatzmaterial mindestens ein Olefin mit 2 bis 12 Kohlenstoffatomen umfasst.

3. Verfahren nach Anspruch 2, bei dem das Einsatzmaterial mindestens ein Alken ausgewählt aus Propen und Butenen umfasst.

4. Verfahren nach einem der vorhergehenden Ansprüche, das unter Verwendung eines Katalysators durchgeführt wird, der ein Molekularsieb vom Strukturtyp MFS umfasst.

5. Verfahren nach Anspruch 4, das mindestens bei 170°C durchgeführt wird.

6. Verfahren nach Anspruch 5, das mindestens bei 220°C durchgeführt wird.

7. Verfahren nach einem der Ansprüche 1 bis 6, bei dem das kristalline Molekularsieb H-ZSM-57 ist.

8. Verfahren nach einem der Ansprüche 1 bis 3, das unter Verwendung eines Katalysators, der ein Molekularsieb vom Typ TON umfasst, bei einer Temperatur von mindestens 200°C durchgeführt wird.

9. Verfahren nach Anspruch 8, das mindestens bei 220°C durchgeführt wird.

10. Verfahren nach Anspruch 9, das mindestens bei 250°C durchgeführt wird.

11. Verfahren nach einem der Ansprüche 1 bis 3 oder einem der Ansprüche 8 bis 10, bei dem das kristalline Molekularsieb H-ZSM-22 ist.

12. Verfahren nach Anspruch 7 oder Anspruch 11, bei dem das kristalline Molekularsieb eine Mischung aus H-ZSM-22 und H-ZSM-57 umfasst.

13. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das kristalline Molekularsieb in Pulverform oder in Form eines Extrudats vorliegt.

14. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Gehalt an schwefelhaltiger Komponente im Bereich von 1 bis 50 Vol.ppm liegt.

15. Verfahren nach Anspruch 14, bei dem der Gehalt im Bereich von 1 bis 30 ppm liegt.

16. Verfahren nach Anspruch 15, bei dem der Gehalt im Bereich von 1 bis 20 ppm liegt.

17. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Schwefelgehalt des Einsatzmaterials reduziert worden ist, bevor das Einsatzmaterial Oligomerisierung unterzogen wird.

18. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die schwefelhaltige Verbindung mindestens eine Verbindung ausgewählt aus Schwefelwasserstoff, Dimethylsulfid, Diethylsulfid, Ethylmethylsulfid, n-Propylsulfid, 1- und 2-Propanthiolen, 1-Butanthiol, 1,1-Methylethylthiol, Ethylmethyldisulfid, Dimethyldisulfid und Tetrahydrothiophen umfasst.

19. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Einsatzmaterial hydratisiert ist.

20. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Einsatzmaterial ein Oligomer ist oder umfasst.

21. Verwendung nach dem Verfahren gemäß Anspruch 1 zur Steuerung des Verzweigungsgrad des Produkts einer Oligomerisierungsreaktion.

22. Verwendung nach dem Verfahren gemäß Anspruch 1 zur Steuerung der Aktivität des Katalysators in einer Oligomerisierungsreaktion.

23. Verfahren nach einem der Ansprüche 1 bis 19, bei dem ferner das Oligomerisierungsprodukt Hydroformylierung unterzogen wird und das Hydroformylierungsprodukt hydriert wird, um einen Alkohol zu produzieren.

24. Verfahren nach Anspruch 23, bei dem ferner der Alkohol verestert wird, um einen Ester zu produzieren.

25. Verfahren nach Anspruch 24, bei dem der Ester des Alkohols mit einer Polycarbonsäure ist und ferner der Ester in eine Weichmacherzusammensetzung eingebracht wird.

26. Verfahren nach Anspruch 25, bei dem die Weichmacherzusammensetzung ferner in eine polymere Zusammensetzung eingebracht wird.

Revendications

1. Procédé pour l'oligomérisation d'une charge de départ oléfinique qui comprend la mise en contact dans des conditions d'oligomérisation d'une charge de départ oléfinique contenant de 1 à 100 ppm en volume de composés contenant du soufre avec un catalyseur comprenant au moins un tamis moléculaire cristallin choisi parmi les tamis des types à structure TON et MFS et la récupération d'un produit contenant au moins un oligomère d'oléfine, le procédé étant mis en oeuvre à une température d'au moins 160 °C à 350 °C et si un tamis du type à structure TON est choisi, d'au moins 190 °C.

2. Procédé selon la revendication 1, dans lequel la charge de départ comprend au moins une oléfine ayant de 2 à 12 atomes de carbone.

3. Procédé selon la revendication 2, dans lequel la charge de départ comprend au moins un alcène choisi parmi le propène et les butènes.

4. Procédé selon une quelconque revendication précédente mis en oeuvre à l'aide d'un catalyseur comprenant un tamis moléculaire de type à structure MFS.

5. Procédé selon la revendication 4, mis en oeuvre à au moins 170 °C.

6. Procédé selon la revendication 5, mis en oeuvre à au moins 220 °C.

7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel le tamis moléculaire cristallin est H-ZSM-57.

8. Procédé selon l'une quelconque des revendications 1 à 3, mis en oeuvre à l'aide d'un catalyseur comprenant un tamis moléculaire de type à structure TON à une température d'au moins 200 °C.

9. Procédé selon la revendication 8, mis en oeuvre à une température d'au moins 220 °C.

10. Procédé selon la revendication 9, mis en oeuvre à une température d'au moins 250 °C.

11. Procédé selon l'une quelconque des revendications 1 à 3 ou l'une quelconque des revendications 8 à 10, dans lequel le tamis moléculaire cristallin est H-ZSM-22.

12. Procédé selon la revendication 7 ou la revendication 11, dans lequel le tamis moléculaire cristallin comprend un mélange de H-ZSM-22 et de H-ZSM-57.

13. Procédé selon une quelconque revendication précédente, dans lequel le tamis moléculaire cristallin est sous forme de poudre ou sous la forme d'un extrudat.

14. Procédé selon une quelconque revendication précédente, dans lequel la teneur en composant contenant du soufre est dans la plage de 1 à 50 ppm en volume.

15. Procédé selon la revendication 14, dans lequel la teneur est dans la plage de 1 à 30 ppm.

16. Procédé selon la revendication 15, dans lequel la teneur est dans la plage de 1 à 20 ppm.

17. Procédé selon une quelconque revendication précédente, dans lequel la teneur en soufre de la charge de départ a été réduite avant de soumettre la charge de départ à l'oligomérisation.

18. Procédé selon une quelconque revendication précédente, dans lequel le composé contenant du soufre comprend au moins un composé choisi parmi le sulfure d'hydrogène, le sulfure de diméthyle, le sulfure de diéthyle, le sulfure d'éthyle et de méthyle, le sulfure de n-propyle, les 1- et 2-propanethiols, le 1-butanethiol, le 1,1-méthyléthylthiol, le disulfure d'éthyle et de méthyle, le disulfure de diméthyle et le tétrahydrothiophène.

19. Procédé selon une quelconque revendication précédente, dans lequel la charge de départ est hydratée.

20. Procédé selon une quelconque revendication précédente dans lequel la charge de départ est ou comprend un oligomère.

21. Utilisation du procédé selon la revendication 1 pour l'ajustement du degré de ramification du produit d'une réaction d'oligomérisation.

22. Utilisation du procédé selon la revendication 1 pour l'ajustement de l'activité du catalyseur dans une réaction d'oligomérisation.

23. Procédé selon l'une quelconque des revendications 1 à 19 comprenant en outre le fait de soumettre le produit d'oligomérisation à une hydroformylation et l'hydrogénation du produit d'hydroformylation pour produire un alcool.

24. Procédé selon la revendication 23 comprenant en outre l'estérification de l'alcool pour produire un ester.

25. Procédé selon la revendication 24, dans lequel l'ester de l'alcool est avec un acide polycarboxylique, comprenant en outre l'incorporation de l'ester dans une composition de plastifiant.

26. Procédé selon la revendication 25 comprenant en outre l'incorporation de la composition de plastifiant dans une composition polymère.